CN103003069B - The manufacture method of the stacked body of polyimide film, the stacked body of polyimide film - Google Patents
The manufacture method of the stacked body of polyimide film, the stacked body of polyimide film Download PDFInfo
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- CN103003069B CN103003069B CN201180036232.7A CN201180036232A CN103003069B CN 103003069 B CN103003069 B CN 103003069B CN 201180036232 A CN201180036232 A CN 201180036232A CN 103003069 B CN103003069 B CN 103003069B
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- China
- Prior art keywords
- polyimide film
- polyamic acid
- stacked body
- base material
- solvent
- Prior art date
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 132
- 238000000034 method Methods 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 95
- 239000000463 material Substances 0.000 claims abstract description 88
- 239000000203 mixture Substances 0.000 claims abstract description 72
- 239000002904 solvent Substances 0.000 claims abstract description 42
- 239000012046 mixed solvent Substances 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002798 polar solvent Substances 0.000 claims abstract description 17
- 239000004642 Polyimide Substances 0.000 claims description 15
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000003252 repetitive effect Effects 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 abstract description 19
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 abstract description 7
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 abstract description 6
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 13
- 239000010410 layer Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 150000004985 diamines Chemical class 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000012856 packing Methods 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000000873 masking effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical class OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000001896 cresols Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000013517 stratification Methods 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000012800 visualization Methods 0.000 description 2
- JRRDISHSXWGFRF-UHFFFAOYSA-N 1-[2-(2-ethoxyethoxy)ethoxy]-2-methoxyethane Chemical compound CCOCCOCCOCCOC JRRDISHSXWGFRF-UHFFFAOYSA-N 0.000 description 1
- WKFQMDFSDQFAIC-UHFFFAOYSA-N 2,4-dimethylthiolane 1,1-dioxide Chemical compound CC1CC(C)S(=O)(=O)C1 WKFQMDFSDQFAIC-UHFFFAOYSA-N 0.000 description 1
- OITMBHSFQBJCFN-UHFFFAOYSA-N 2,5,5-trimethylcyclohexan-1-one Chemical compound CC1CCC(C)(C)CC1=O OITMBHSFQBJCFN-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XDYLWBWPEDSSLU-UHFFFAOYSA-N 4-(3-carboxyphenyl)benzene-1,2,3-tricarboxylic acid Chemical class OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C(C(O)=O)=CC=2)C(O)=O)=C1 XDYLWBWPEDSSLU-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000009750 centrifugal casting Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
- C09D177/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03926—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0393—Flexible materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E10/00—Energy generation through renewable energy sources
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31721—Of polyimide
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Abstract
The invention provides the manufacture method of the stacked body of polyimide film, wherein, the polyamic acid solution composition comprising polyamic acid and the specific mixed solvent be made up of specific chemical composition is coated base material, next, heats under given conditions.The manufacture method of the stacked body of polyimide film, wherein, the film be made up of polyamic acid solution composition is formed at substrate surface, obtain the duplexer formed by base material and polyamic acid solution composition, next the duplexer formed by above-mentioned base material and polyamic acid solution composition is at least being greater than 150 DEG C and the temperature range being less than 200 DEG C heats after more than 10 minutes, the temperature range being 400 ~ 550 DEG C in maximum temperature heats, obtain the duplexer formed by base material and polyimide film, in polyamic acid solution composition, employ 3, 3 ', 4, 4 '-bibenzene tetracarboxylic dianhydride and/or pyromellitic acid anhydride, comprising organic polar solvent with the polyamic acid of p-phenylenediamine (PPD) and be dissolve in the mixed solvent of 5 ~ 35 quality % with the ratio of the solvent of water azeotropic with the solvent of water azeotropic and all in solvent.
Description
With the relation of association request
The application of this part requires based on the application of the priority of No. 2010-165366, the Patent of applying for the Japan Patent Room on July 22nd, 2010, the disclosure of this application also by referring to and comprise wherein.
Technical field
The present invention relates to the manufacture method being laminated with the stacked body of polyimide film of polyimide film at base material.Especially, relate to the manufacture method of the stacked body of polyimide film, it is characterized in that, comprise the polyamic acid solution composition of polyamic acid and the specific mixed solvent be made up of specific chemical composition in base material coating, secondly the duplexer obtained is heated under given conditions.
Background technology
Employ 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (is also abbreviated as s-BPDA below sometimes.) and/or pyromellitic acid anhydride (be also sometimes abbreviated as PMDA below.) as tetrabasic carboxylic acid composition, employ p-phenylenediamine (PPD) and (be also sometimes abbreviated as PPD below.) as the polyimides of diamine component, due to excellences such as heat resistance, mechanical strength, dimensional stabilitys, therefore use in a variety of applications where.
But, the polyamic acid solution composition be made up of is coated base material, heat the duplexer that will obtain being formed by base material and polyimide film, easily bubble, protrude, mouldability has problems this chemical composition.Therefore, the polyimide film be made up of this chemical composition is usually adopted and is obtained with the following method: polyamic acid solution composition is coated base material, by the film heat drying obtained, makes self-supporting film, next after self-supporting film being peeled off from base material, and then carry out adding hot-imide process.
On the other hand, the polyamic acid solution composition be made up of this chemical composition is coated base material, heating will obtain the duplexer formed by base material and polyimide film, except the problem of such mouldability of easily bubbling, protrude, there is the problem that the characteristics such as the heat resistance of the polyimide film obtained easily reduce.Especially, when polyamic acid solution composition that employ process easy, applicable easily formation film, that comprise the lower polyamic acid of molecular weight ratio, there is the problem that the characteristics such as the heat resistance of the polyimide film obtained reduce further.
In patent document 1, describe by making a part for above-mentioned chemical composition become specific composition, the reduction of rejection characteristic, improves the manufacture method of the polyimide film of mouldability simultaneously.
In patent document 2, describe the mixed solvent being combined with specific organic polar solvent by making the solution of the polyamic acid solution composition be made up of above-mentioned chemical composition become, thus can mouldability be improved, obtain the manufacture method of the polyimide film of the polyimide film of excellent.
In these documents, for solvent, preferably use the Organic polar solvent dissolved by polyamic acid, do not record for these solvents with the mixed solvent of the solvent of water azeotropic.
Describe in patent document 3: in order to adjust imide ring closure degree, the water produced with imidizate is rejected to outside system, therefore also can heat under the state be present at the material making molecular sieve etc. have dehydration in resin liquid, or heat under the existence of the azeotropic solvents such as toluene, or more than 1 or 2 combination of the method under reduced pressure heated etc. is carried out.
In patent document 4; describe the precursor being coated with polyimides at the support substrates such as glass (base material); add hot-imide process; form heat resistant substrates substrate (polyimide film); next; laminating transparent electrode layer, amorphous silicon layer, back electrode layer etc. thereon; and then after formation protective layer; peel off between support substrate and heat resistant substrates substrate; obtain that there is flexual thin-film solar cells; if the heating described when forming heat resistant substrates substrate (polyimide film) is insufficient, when forming amorphous silicon layer, likely there is degassed problem.
In patent document 4, in order to solve the problem, propose with polyimide film with for forming heat resistant substrates substrate by 2 layers of its bonding stripping resin bed (polyamic acid).But 2 stratification increase due to operation, therefore uneconomical and control also to become complicated.In addition, peel off resin bed owing to must be formed with polyamic acid, same problem when therefore forming polyimide film fails fully to solve.
Prior art document
Patent document 1: JP 2007-332369 publication
Patent document 2: JP 2009-91573 publication
Patent document 3: Unexamined Patent 3-157427 publication
Patent document 4: Unexamined Patent 5-315630 publication
Summary of the invention
The object of the invention is to the manufacture method proposing the stacked body of polyimide film, wherein, to 3 be employed, 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride and/or pyromellitic acid anhydride as tetrabasic carboxylic acid composition, employ after p-phenylenediamine (PPD) coats base material as the polyamic acid solution composition of diamine component and heat, can suppress to bubble, protrude, obtain the duplexer formed by base material and polyimide film good forming ability.The characteristics such as the heat resistance of the polyimide film of this duplexer are good, when the stacked further other materials of the polyimide film of this duplexer, can suppress to result from the problem such as degassed of polyimide film.
The present invention relates to following every.
(1) manufacture method of the stacked body of polyimide film, it is characterized in that, the film be made up of polyamic acid solution composition is formed at substrate surface, obtain the duplexer formed by base material and polyamic acid solution composition, next the duplexer formed by above-mentioned base material and polyamic acid solution composition is at least being greater than 150 DEG C and the temperature range being less than 200 DEG C heats after more than 10 minutes, the temperature range being 400 ~ 550 DEG C in maximum temperature heats, obtain the duplexer formed by base material and polyimide film, in polyamic acid solution composition, the polyamic acid with the repetitive shown in following chemical formula (1) is comprising organic polar solvent and with the solvent of water azeotropic and all in solvent is being dissolve in the mixed solvent of 5-35 quality % with the ratio of the solvent of water azeotropic.
[changing 1]
[unit of more than the 75 % by mole unit for 4 valencys based on biphenyl structural shown in following chemical formula (2) of A of chemical formula (1) and/or 4 valencys based on benzene ring structure shown in following chemical formula (3), more than the 75 % by mole unit for the divalent based on phenyl structure shown in following chemical formula (4) of the B of chemical formula (1).]
[changing 2]
[changing 3]
[changing 4]
(2) manufacture method of the stacked body of polyimide film described in above-mentioned item 1, is characterized in that, the log viscosities of the polyamic acid of polyamic acid solution composition is below 2.0dL/g.
(3) manufacture method of the stacked body of the polyimide film described in above-mentioned item 1 or 2, is characterized in that, the thickness of the polyimide film obtained is less than 40 μm.
(4) manufacture method of the stacked body of the polyimide film described in any one of above-mentioned item 1 ~ 3, it is characterized in that, at the further stacked other materials of the polyimide film surface of the stacked body of polyimide film, obtain the stacked body of polyimide film formed by base material and polyimide film and other materials.
(5) manufacture method of the stacked body of polyimide film described in above-mentioned item 4, it is characterized in that, from the polyimide film stacked body formed by base material and polyimide film and other materials, base material is separated, obtains the stacked body of polyimide film formed by polyimides and other materials.
(6) the stacked body of the polyimide film formed by base material and polyimide film, is characterized in that, adopts the manufacture method described in any one of above-mentioned item 1 ~ 4 to obtain.
(7) the stacked body of polyimide film, is characterized in that, the surface of the polyimide film of the stacked body of polyimide film described in above-mentioned item 6 is stacked further other materials.
(8) duplexer of polyimide film and other materials, is characterized in that, is isolated by base material from the polyimide film stacked body described in above-mentioned item 7.
The manufacture method of the stacked body of polyimide film according to the present invention, to 3 be employed, 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride and/or pyromellitic acid anhydride as tetrabasic carboxylic acid composition, employ after p-phenylenediamine (PPD) coats base material as the polyamic acid solution composition of diamine component and heat, can suppress to bubble, protrude and good forming ability obtain the duplexer that formed by base material and polyimide film.The characteristics such as the heat resistance of the polyimide film of this duplexer are good, when the stacked further other materials of the polyimide film of this duplexer, can suppress to result from the problem such as degassed of polyimide film.
Detailed description of the invention
The polyamic acid composition used in manufacture method of the present invention comprises polyamic acid as polyimide precursor, and this polyamic acid is the polyamic acid with the repetitive shown in above-mentioned chemical formula (1).Namely, form more than 75 % by mole of tetrabasic carboxylic acid composition of polyamic acid, preferably more than 80 % by mole, more preferably more than 90 % by mole, particularly preferably 100 % by mole are by 3,3 ', 4,4 '-biphenyl tetracarboxylic acids and/or Pyromellitic Acid class composition, more than 75 % by mole of diamine component, preferably more than 80 % by mole, more preferably more than 90 % by mole, particularly preferably 100 % by mole are made up of p-phenylenediamine (PPD).
Further, so-called 3,3 ', 4,4 '-biphenyl tetracarboxylic acids or Pyromellitic Acid class are these tetrabasic carboxylic acids, these acid anhydrides, these the carboxylate etc. of alcohol can form the material of the tetrabasic carboxylic acid composition of polyamic acid.
In the present invention, as 3,3 ', 4, tetrabasic carboxylic acid composition beyond 4 '-biphenyl tetracarboxylic acids and/or Pyromellitic Acid class, and indefinite, preferably can illustrate 2,3,3 ', 4-biphenyl tetracarboxylic acids, 3,3 ', 4,4 '-benzophenone tetracarboxylic class, 2,3,6,7-naphthalenetetracarbacidic acidic class, 4,4 '-oxygen di-O-phthalic acids, 3,3 ', 4,4 '-diphenyl sulfone tetramethyl acids etc.
In the present invention, as the diamine component beyond p-phenylenediamine (PPD), and indefinite, preferably can illustrate m-phenylene diamine (MPD), diamino-diphenyl ether, diaminotoluene, diaminonaphthalene, diaminodiphenyl-methane, diamino diphenyl sulfone etc.
The preparation of polyamic acid preferably can adopt existing known method, the condition of preparing polyamic acid.Therefore, be not particularly limited, preferably, such as by tetracarboxylic dianhydride and diamines, in organic solvent, under the solid point concentration converted at polyimides is the concentration of 5 ~ 50 quality % degree, in order to the amido link and carboxyl that suppress polyamic acid carry out imidizate, the temperature conditions of preferably less than 100 DEG C, more preferably less than 80 DEG C stirs 0.1 below littlely makes it react up to tens hours limits, obtains as homogeneous polyamic acid solution.If the solid point concentration that polyimides converts is less than 5 quality %, use a large amount of solvents, therefore uneconomical, if solid point concentration is more than 50 quality %, become high viscosity, there is the tendency that process waits change difficult.
As the organic polar solvent of the preparation for polyamic acid, can preferably use known organic polar solvent.Preferably can use such as METHYLPYRROLIDONE, N, dinethylformamide, N, the organic polar solvent such as N-dimethylacetylamide, cresols, N, N-dimethyl sulfoxide (DMSO), N-methyl caprolactam, methyl triglyme, methyl diglycol dimethyl ether, sulfolane.In addition, as the organic solvent of the preparation for polyamic acid, the mixed solvent of the formation polyamic acid solution composition used in manufacture method of the present invention can be used for reaction dissolvent in advance.For above-mentioned mixed solvent by aftermentioned.
The molecular weight of the polyamic acid contained in the polyamic acid solution composition used in the present invention is not particularly limited.
Usually, when manufacturing polyimide film, in order to realize sufficient characteristic, use the polyamic acid that log viscosities is higher more than the molecular weight ratio of 2.0dL/g.On the other hand, when to employ log viscosities be the molecular weight ratio of below 2.0dL/g lower polyamic acid, be difficult to form the polyimide film meeting the characteristic that should be obtained by this chemical composition.Especially, the polyimide film also showing high-fire resistance (suppress thermal decomposition, degassed generation is few) is difficult to be formed in the temperature province of more than 500 DEG C.
But, by adopting the present invention, even if when employ the log viscosities usually do not used be below 2.0dL/g, preferably below 1.5dL/g, more preferably below 1.0dL/g, particularly preferably below 0.8dL/g and more than 0.2dL/, polyamic acid that preferably molecular weight ratio of more than 0.3dL/g is lower, can realize being formed in the temperature province of more than 500 DEG C the polyimide film also showing high-fire resistance (suppress thermal decomposition, degassed generation is few) and become easily so particularly preferred effect.
Have again, the stability of solution of polyamic acid solution composition of the present invention is good, and there is not the precipitation of component of polymer, the gelation of solution, keep in the scope of homogeneous solution state, the amido link of polyamic acid and a part for carboxyl can imidizates.
As the mixed solvent of the polyamic acid solution composition used in manufacture method of the present invention, use and comprise organic polar solvent and the solvent with water azeotropic, being more than 5 quality %, preferably more than 10 quality % with the ratio of the solvent of water azeotropic and being the mixed solvent of below 35 quality %, preferably below 30 quality %, more preferably below 25 quality % in whole solvent.If be less than 5 quality % with the ratio of the solvent of water azeotropic all in solvent, can not improve mouldability fully, if more than 35 quality %, cannot dissolve equably, the stability of solution of polyamic acid solution composition declines, therefore not preferred.
As the organic polar solvent in mixed solvent, preferably can use the known organic polar solvent of the preparation that can be used in polyamic acid, such as N can be enumerated, dinethylformamide, N, N-dimethylacetylamide, METHYLPYRROLIDONE, the amide solvents such as N-methyl caprolactam, dimethyl sulfoxide (DMSO), hexamethyl phosphoramide, dimethyl sulfone, sulfolane, the solvent containing sulphur atom such as dimethylsulfolane, cresols, phenol, the phenol solvents such as xylenols, the lactone solvents such as gamma-butyrolacton, isophorone, cyclohexanone, 3, 3, the ketones solvents etc. such as 5-trimethylcyclohexanone, preferred aprotic organic polar solvent, more preferably boiling point is the aprotic organic polar solvent of more than 180 DEG C.Further, in the present invention, not containing the solvent with water azeotropic in organic polar solvent.
As the solvent with water azeotropic, as long as with the solvent of water azeotropic, preferably can enumerate such as toluene, dimethylbenzene, pyridine etc. and there is the hydrocarbon compound of aromatic rings or the compound etc. containing heterocycle.With (as pure material) boiling point preferably more than 100 DEG C of the solvent of water azeotropic, be less than 180 DEG C, more preferably more than 110 DEG C, be less than 170 DEG C.
As the combination of mixed solvent of the present invention, especially, as organic polar solvent, use from N, dinethylformamide, N, more than one the organic polar solvent selected in N-dimethylacetylamide, METHYLPYRROLIDONE, as the solvent with water azeotropic, uses more than one the solvent selected from toluene, dimethylbenzene, pyridine to be preferred.
In the present invention, make the method for mixed solvent, it can be the method that the product former state using mixed solvent to modulate at first when preparing polyamic acid solution composition is used, or only use organic polar solvent when can be and prepare polyamic acid solution composition, in the polyamic acid solution composition obtained, add ormal weight with solvent that is water azeotropic, the method mixed equably.In addition, can also be after preparing polyamic acid for the moment, adopt the polyamic acid obtained to drop in the poor solvent of the such polyamic acid of such as methyl alcohol and make it separate out (precipitation) such method to emanate, next make this polyamic acid be dissolved in method in mixed solvent of the present invention.
The polyamic acid composition used in manufacture method of the present invention, the solid point concentration preferably using polyimides to convert is the polyamic acid composition of 5 ~ 50 quality %, preferably 10 ~ 45 quality %, the more preferably concentration of 15 ~ 40 quality %.If solid point concentration is less than 5 quality %, use a large amount of solvents, therefore uneconomical, if solid point concentration is more than 50 quality %, at room temperature become high viscosity, there is process when coating base material etc. and become difficult tendency.
The polyamic acid solution composition used in the present invention comprises as the above-mentioned polyamic acid of polyimide precursor, the above-mentioned mixed solvent that dissolved, and then as required, inorganic or the organic filler material that micro-powdered silica, boron nitride, aluminium oxide, carbon black etc. are fine can be coordinated, in addition, other gradation composition can also be coordinated as required.As other gradation composition, according to purposes, require that performance determines, can preferably coordinate the conductive agent such as colouring agent, metal powder, releasing agent, surface conditioning agent, viscosity modifier, coupling agent, the surfactants etc. such as plasticizer, weather resisting agent, antioxidant, heat stabilizer, lubricant, antistatic additive, brightening agent, dyestuff, pigment.These gradation compositions can be matched with liquid composite in advance, also can add in use with the use of.
If further, coordinate fine packing material in polyamic acid solution composition, easily suppress the generation of the foaming in film making process, protrusion, therefore sometimes in the raising of mouldability, become favourable.Employ in the manufacture method of the polyimide film of polyamic acid solution composition of the present invention, if the polyamic acid solution composition of the packing material that collaboration is fine, the foaming that packing material produces, the inhibition of protrusion and the inhibition of foaming produced with mixed solvent collaborative, mouldability improves further.Even if coordinate fine packing material, when not using mixed solvent, the raising of masking may not be abundant, has limit thickness, film forming condition, because of thickness, film forming condition, can not thoroughly suppress to bubble.In addition, easily there is such as film during masking and the other problems such as to crack.
The manufacture method of the stacked body of polyimide film of the present invention, it is characterized in that, the film formed by above-mentioned polyamic acid solution composition is formed at substrate surface, obtain the duplexer formed by base material and polyamic acid solution composition, next by the duplexer formed by above-mentioned base material and polyamic acid solution composition at least more than 150 DEG C ~ temperature range that is less than 200 DEG C heats after more than 10 minutes, the temperature range being 400 ~ 550 DEG C in maximum temperature heats, and obtains the duplexer formed by base material and polyimide film.
In the present invention, so-called base material, be surface coating polyamic acid, the parts of film can be formed, as long as have substantially do not make liquids and gases through compact texture, shape, material are not particularly limited, according to its purposes, various base material can be adopted.
The film formation base materials such as himself known band, roller or the mould that use when can be common manufacture film; also can be form circuit substrate, the electronic unit of polyimide film as diaphragm etc. on its surface; parts, the goods of tunicle are formed, the film etc. of side during formation polyimide film formation multiple stratification film on the surface of slide unit etc.In addition, in the present invention, so-called base material, preferably, can be as described in Patent Document 3 at glass plate coating polyamic acid solution composition, add hot-imide process, form the stacked body of polyimide film, next, thereon further the other materials such as stacked such as transparent electrode layer, amorphous silicon layer, back electrode layer time the glass plate that uses.
As the method for the coating when substrate surface forms the film formed by polyamic acid solution composition, himself known method such as such as spraying process, print roll coating method, method of spin coating, bar type rubbing method, ink-jet method, silk screen print method, slot coated (ス リ ッ ト コ ー ト) method suitably can be adopted.At the film of the polyamic acid solution composition formation that substrate surface is formed, the method heated at relatively low temperatures under can adopting such as decompression carries out deaeration.
In the manufacture method of the stacked body of polyimide film of the present invention, the duplexer that the base material of such formation and polyamic acid solution composition are formed at least more than 150 DEG C, preferably greater than 160 DEG C, more preferably above 160 DEG C, be less than 200 DEG C, be preferably less than 195 DEG C, be more preferably less than the temperature range of 190 DEG C, heat more than 10 minutes, preferably more than 20 minutes, more preferably more than 30 minutes, usual less than 3 hours, preferably less than 2 hours.Next, maximum temperature be more than 400 DEG C, preferably more than 420 DEG C, more preferably more than 450 DEG C, below less than 550 DEG C, preferably 500 DEG C, the more preferably temperature range of less than 480 DEG C, and indefinite but heat 0.01 ~ 3 hour, preferred 0.1 ~ 1 hour degree, make polyamic acid solution composition become polyimide film, thus obtain the duplexer that formed by base material and polyimide film.
The heating of the manufacture method of the stacked body of polyimide film of the present invention, as long as meet above-mentioned heating condition, other conditions are not particularly limited, solvent to be removed at the lower temperature of less than 140 DEG C below 150 DEG C, preferably preferably at first as far as possible, next, temperature is gently brought up to the heating of the stage of the highest heat treatment temperature.The thickness that such heating condition particularly corresponds to polyimide film suitably determines to be advisable.
Therefore, such as, initial less than 150 DEG C, preferably at the lower temperature of less than 140 DEG C by after solvent removing, be greater than 150 DEG C and the temperature range being less than 200 DEG C heats more than 10 minutes, and then more than 200 DEG C and after being less than 400 DEG C, preferably heating at the temperature of less than 300 DEG C, maximum temperature be more than 400 DEG C, the preferred temperature range of less than 500 DEG C, and indefinite but heat 0.01 ~ 3 hour, make polyamic acid solution composition become polyimide film, this is a kind and preferably heats.
Further, in the manufacture method of the stacked body of polyimide film of the present invention, be not particularly limited the thickness of base material and polyimide film, the thickness of polyimide film is preferably 1 ~ 150 μm, be more preferably 1 ~ 50 μm, more preferably 1 ~ 40 μm, be particularly preferably 1 ~ 30 μm of degree.If thickness is thickening, more easily protrude, bubble, therefore in order to suppress it to occur, sometimes carry out the drying removing of the solvent of longer time or make the time of heating, programming rate condition that is longer, that to carry out etc. lentamente select to become necessary, production efficiency reduces.Therefore, for the manufacture method of the stacked body of polyimide film of the present invention, the thickness of the polyimide film preferably obtained is less than 40 μm, preferably less than 30 μm.
The manufacture method of the stacked body of polyimide film of the present invention, utilizes stable masking (mouldability), can obtain the stacked body of polyimide film formed with the polyimide film with high characteristic by base material.And, be necessary at the further stacked other materials of the polyimide film surface of the stacked body of this polyimide film, when further other materials being heated, compared with heating condition when manufacturing polyimide film, even if under harsher condition (the higher temperature conditions of such as 500 DEG C ~ 600 DEG C), the characteristics such as the heat resistance of polyimide film are also stablized, and there is not the problems such as degassed, therefore extremely preferred.
Have again, if use the stacked body of polyimide film of the present invention, preferably can obtain the stacked body of polyimide film formed by base material and polyimides and other materials being laminated with other materials at polyimide film surface further, and then from the polyimide film stacked body formed by base material and polyimides and other materials, base material is separated, also preferably can obtain the stacked body of polyimide film formed by polyimides and other materials.So-called other materials, is not particularly limited, preferably can illustrates functional film etc. that transparent electrode layer, amorphous silicon layer, back electrode layer etc. are formed by inorganic material, metal material.The stacked body of polyimide film of the polyimides and other materials formation that are laminated with such other materials can be preferably used as the parts of solar cell, display unit etc.
In addition, manufacture method of the present invention improves masking (mouldability), and can obtain having the polyimide film of above-mentioned extremely excellent mechanical property, therefore at face film, with the copper-clad laminated substrate such as stacked 2 layers of CCL obtained of Copper Foil, be particularly applied in seamless-band that centrifugal casting etc. obtains etc. and can preferably adopt.
Seamless-band, except using the inner peripheral surface of cylindric mould or outer peripheral face as base material, being filmed beyond the aspect of (shaping) while make mould rotate limit, can preferably adopting aforesaid film-forming method, film forming condition.But, the usual thickness of seamless-band is thicker, and (common thickness is more than 40 μm, particularly 50 ~ 150 μm of degree), and the situation containing packing material is more in large quantities many, drying removing or longer, to carry out the time, programming rate etc. of heating the lentamente condition of therefore carrying out the solvent of longer time are selected to be applicable to.
In addition, for seamless-band, various packing materials etc. are coordinated according to its purposes.Gradation composition preferably carries out by adding cooperation in polyamic acid solution.In addition, can coordinate in advance in solution before the reaction when preparing polyamic acid solution.
Such as, the annular tube shaped band of polyimides as duplicator fixing band use time, in order to improve thermal conductivity, preferably coordinate silica, boron nitride, aluminium oxide etc.In addition, in order to prevent toner melt bonded in surface attachment, also can at the layer of the stacked non-adhesive formed by fluororesin such as polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoraoethylene-hexafluoropropylene copolymers of belt surface.
In addition, when the annular tube shaped band of polyimides uses as the transfer belt of duplicator, in order to give semiconduction, preferably carbon black etc. is coordinated.
Embodiment
The present invention is described in more detail below to use embodiment.Further, the present invention is not limited to following embodiment.
The dummy suffix notation of the compound used in following embodiment is as described below.
PPD: p-phenylenediamine (PPD)
S-BPDA:3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride
The evaluation method assay method used in following embodiment is as described below.
(log viscosities of liquid composite)
Log viscosities (η
inh) be, by modulation, polyamic acid solution is dissolved in METHYLPYRROLIDONE equably to make polyamic acid concentration for the solution of 0.5g/100 milliliter solvent, for this solution, at 30 DEG C, use キ ャ ノ Application Off ェ Application ス ケ No.100, measure and flow down time (T
1).Log viscosities is by using the time that the flows down (T of the solvent of contrast
0), calculated by following formula.Unit is dL/g.
Log viscosities={ ln(T
1/ T
0)/0.5
(solid divides concentration)
The solid point concentration of polyamic acid solution is by polyamic acid solution at 350 DEG C dry 30 minutes, the value obtained by following formula by the weight W1 before drying and dried weight W2.
Solid divides concentration (% by weight)={ (W1-W2)/W1 } × 100
(solution viscosity)
Use ト キ メ ッ Network society E type viscosimeter, the solution viscosity at measuring 30 DEG C.
(stability of solution of polyamic acid solution composition)
The stability of solution of polyamic acid solution is passed through for the polyamic acid solution being modulated to monomer concentration 20%, and the change using E type viscosimeter to measure solution viscosity at 30 DEG C is evaluated.Namely, the solution viscosity of polyamic acid solution at once after modulation is designated as P1, P2 is designated as by placing the solution viscosity measured afterwards for 90 days under the atmosphere of 5 DEG C, the situation of the rate of change of the solution viscosity obtained by following formula below ± 10% is designated as zero (good), by becoming ± situation of more than 10% is designated as × (bad).
Rate of change (%)={ (P2-P1)/P1 } × 100
(evaluation ［ TGA assay method ］ of degassed incidence)
The TG-DTA2000S of the apparatus for thermal analysis using Co., Ltd. マ ッ Network サ イ エ Application ス society to manufacture, heats up with 10 DEG C/min to 600 DEG C from room temperature (25 DEG C), calculates the weight reduction rates in each temperature province.Result from degassed generation owing to thinking that this weight reduces, therefore in the present invention, the index of this weight reduction rates as degassed incidence is evaluated.
(evaluation of protrusion)
Manufacture the polyimide film of 10cm × 10cm on a glass, the surface of the polyimide film that visualization obtains.Observe the region creating protrusion, the situation that there is not the region creating protrusion is designated as A(good), the situation being less than 30% of the gross area by the region creating protrusion is designated as in the middle of B(), it is bad that the situation region creating protrusion being exceeded 30% of the gross area is designated as C().
[embodiment 1]
Possess agitator, nitrogen import discharge pipe internal volume 500ml glass reaction vessel in, add the 400.0g of the METHYLPYRROLIDONE as solvent, add the 26.8801g(0.2485 mole of PPD wherein) and the 73.1199g(0.2485 mole of s-BPDA), stir 10 hours at 50 DEG C, obtain the polyamic acid solution of solid point concentration 18.7%, solution viscosity 5Pas, log viscosities 0.65.11 quality % in the whole quantity of solvent of dimethylbenzene 50.0g(are added in this polyamic acid solution composition), obtain the polyamic acid solution composition of homogeneous dissolving.
Bar coaters is adopted to be applied on the glass plate of base material by this polyamic acid solution composition, by this film at 120 DEG C, 150 DEG C at each 10 minutes, 180 DEG C at 60 minutes, 200 DEG C, 250 DEG C at each 10 minutes, 450 DEG C 30 minutes, heat, obtain the duplexer formed by the polyimide film of glass plate and thick 10 μm.
After visualization is carried out to the outward appearance of the polyimide film surface of duplexer, carry out TGA mensuration, measure the index of the weight reduction rates in the temperature range of 500 ~ 550 DEG C, 550 ~ 600 DEG C as the evaluation of degassed incidence.
Show the result in table 1.
[embodiment 2 ~ 7]
As shown in table 1, change beyond the kind of mixed solvent, ratio, heating condition, carried out operation similarly to Example 1.
Show the result in table 1.
[comparative example 1 ~ 6]
As shown in table 2, change beyond the kind of mixed solvent, ratio, heating condition, carried out operation similarly to Example 1.
Show the result in table 2.
industry utilizes possibility
Adopt the manufacture method of the stacked body of polyimide film of the present invention, to 3 be employed, 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride and/or pyromellitic acid anhydride as tetrabasic carboxylic acid composition, employ after p-phenylenediamine (PPD) coats base material as the polyamic acid solution composition of diamine component and heat, can suppress to bubble, protrude, obtain the duplexer formed by base material and polyimide film good forming ability.The characteristics such as the heat resistance of the polyimide film of this duplexer are good, when the stacked further other materials of the polyimide film of this duplexer, can suppress to result from the problem such as degassed of polyimide film.
Claims (7)
1. the manufacture method of the stacked body of polyimide film, it is characterized in that, the film be made up of polyamic acid solution composition is formed at substrate surface, obtain the duplexer formed by base material and polyamic acid solution composition, next the duplexer formed by above-mentioned base material and polyamic acid solution composition is at least being greater than 160 DEG C and the temperature range being less than 200 DEG C heats after more than 10 minutes, the temperature range being 400 ~ 550 DEG C in maximum temperature heats, obtain the duplexer formed by base material and polyimide film, in polyamic acid solution composition, the polyamic acid with the repetitive shown in following chemical formula (1) is comprising organic polar solvent and with the solvent of water azeotropic and all in solvent is being dissolve in the mixed solvent of 5 ~ 35 quality % with the ratio of the solvent of water azeotropic, the log viscosities of above-mentioned polyamic acid is below 1.0dL/g, with the solvent of water azeotropic by there is the hydrocarbon of aromatic rings or forming containing the compound of heterocycle,
The unit of more than the 75 % by mole unit for 4 valencys based on biphenyl structural shown in following chemical formula (2) of A of chemical formula (1) and/or 4 valencys based on benzene ring structure shown in following chemical formula (3), more than the 75 % by mole unit for the divalent based on phenyl structure shown in following chemical formula (4) of the B of chemical formula (1)
2. the manufacture method of the stacked body of polyimide film according to claim 1, is characterized in that, the thickness of the polyimide film obtained is less than 40 μm.
3. the manufacture method of the stacked body of the polyimide film described in claim 1 or 2, it is characterized in that, at the further stacked other materials of the polyimide film surface of the stacked body of polyimide film, obtain the stacked body of polyimide film formed by base material and polyimide film and other materials.
4. the manufacture method of the stacked body of polyimide film according to claim 3, it is characterized in that, from the polyimide film stacked body formed by base material and polyimide film and other materials, base material is separated, obtains the stacked body of polyimide film formed by polyimides and other materials.
5. the stacked body of the polyimide film formed by base material and polyimide film, is characterized in that, adopts the manufacture method described in any one of claims 1 to 3 to obtain.
6. the stacked body of polyimide film, is characterized in that, is laminated with other materials further on the surface of the polyimide film of the stacked body of polyimide film according to claim 5.
7. the duplexer of polyimide film and other materials, is characterized in that, is isolated by base material from polyimide film according to claim 6 stacked body.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010165366 | 2010-07-22 | ||
| JP2010-165366 | 2010-07-22 | ||
| PCT/JP2011/067175 WO2012011607A1 (en) | 2010-07-22 | 2011-07-21 | Process for production of polyimide film laminate, and polyimide film laminate |
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| Publication Number | Publication Date |
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| CN103003069A CN103003069A (en) | 2013-03-27 |
| CN103003069B true CN103003069B (en) | 2015-12-16 |
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| CN201180036232.7A Active CN103003069B (en) | 2010-07-22 | 2011-07-21 | The manufacture method of the stacked body of polyimide film, the stacked body of polyimide film |
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| US (1) | US9187676B2 (en) |
| EP (1) | EP2596949A4 (en) |
| JP (1) | JP5510545B2 (en) |
| KR (1) | KR101538559B1 (en) |
| CN (1) | CN103003069B (en) |
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| US8679341B2 (en) | 2005-05-06 | 2014-03-25 | Fujifilm Corporation | Method of concentrating nanoparticles and method of deaggregating aggregated nanoparticles |
| KR101892783B1 (en) * | 2011-06-14 | 2018-08-28 | 우베 고산 가부시키가이샤 | Method for producing polyimide laminate, and polyimide laminate |
| WO2013157565A1 (en) * | 2012-04-19 | 2013-10-24 | 宇部興産株式会社 | Thermal adhesive polyimide film, method for producing thermal adhesive polyimide film, and polyimide/metal laminate using thermal adhesive polyimide film |
| JP6445965B2 (en) * | 2013-02-19 | 2018-12-26 | 日鉄ケミカル＆マテリアル株式会社 | LAMINATE, SOLAR CELL MEMBER, SOLAR CELL, DISPLAY DEVICE MEMBER, DISPLAY DEVICE AND LAMINATE MANUFACTURING METHOD |
| CN105246686B (en) * | 2013-05-28 | 2017-12-01 | 旭硝子株式会社 | Flexible substrate and its manufacture method, glass laminate and its manufacture method, the manufacture method of electronic equipment |
| CN103327135A (en) * | 2013-06-27 | 2013-09-25 | 贝壳网际（北京）安全技术有限公司 | Domain name resolution method, device and client |
| US9219515B2 (en) | 2013-09-05 | 2015-12-22 | Apple Inc. | Protective film and related assembly and method |
| JP2017113880A (en) * | 2014-04-28 | 2017-06-29 | 旭硝子株式会社 | Glass laminate, glass substrate with resin layer, and support base material with resin layer |
| CN109422876A (en) * | 2017-08-28 | 2019-03-05 | 苏州聚萃材料科技有限公司 | Solution, Kapton and its application of polyamic acid |
| CN111435688B (en) * | 2018-12-25 | 2021-11-23 | 苏州阿特斯阳光电力科技有限公司 | Photovoltaic backboard and photovoltaic module comprising same |
| CN112111219B (en) * | 2019-06-20 | 2023-04-14 | 东京应化工业株式会社 | Varnish composition, precursor film of polyimide porous film, method for producing precursor film of polyimide porous film, and method for producing polyimide porous film |
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| CN101679632A (en) * | 2007-03-29 | 2010-03-24 | 宇部兴产株式会社 | Aromatic polyimide and process for production thereof |
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| JPS61111359A (en) | 1984-11-06 | 1986-05-29 | Ube Ind Ltd | Polyamic acid solution composition and polyimide film |
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| US5741598A (en) | 1995-08-01 | 1998-04-21 | Ube Industries, Ltd. | Polyimide/metal composite sheet |
| CA2274264C (en) * | 1996-12-05 | 2006-11-07 | E.I. Du Pont De Nemours And Company | Polyimides having high tg, high tos, and low moisture regain |
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- 2011-07-21 EP EP11809768.2A patent/EP2596949A4/en not_active Withdrawn
- 2011-07-21 CN CN201180036232.7A patent/CN103003069B/en active Active
- 2011-07-21 JP JP2012525460A patent/JP5510545B2/en active Active
- 2011-07-21 WO PCT/JP2011/067175 patent/WO2012011607A1/en active Application Filing
- 2011-07-21 US US13/810,489 patent/US9187676B2/en not_active Expired - Fee Related
- 2011-07-21 KR KR1020137001617A patent/KR101538559B1/en active IP Right Grant
- 2011-07-22 TW TW100126007A patent/TWI573690B/en active
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| US5115090A (en) * | 1990-03-30 | 1992-05-19 | Sachdev Krishna G | Viscosity stable, essentially gel-free polyamic acid compositions |
| CN101679632A (en) * | 2007-03-29 | 2010-03-24 | 宇部兴产株式会社 | Aromatic polyimide and process for production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| US9187676B2 (en) | 2015-11-17 |
| KR101538559B1 (en) | 2015-07-29 |
| JPWO2012011607A1 (en) | 2013-09-09 |
| CN103003069A (en) | 2013-03-27 |
| EP2596949A1 (en) | 2013-05-29 |
| TWI573690B (en) | 2017-03-11 |
| KR20130029805A (en) | 2013-03-25 |
| US20130115473A1 (en) | 2013-05-09 |
| WO2012011607A1 (en) | 2012-01-26 |
| TW201213130A (en) | 2012-04-01 |
| JP5510545B2 (en) | 2014-06-04 |
| EP2596949A4 (en) | 2014-01-15 |
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